Perfluoroadamantyl acrylate compound and intermediate therefor

ABSTRACT

A perfluoroadamantyl acrylate compound which is highly useful as a raw material for functional resins,etc.;and an intermediate therefore. The perfluoroadamantyl acrylate compound comprises perfluoroadamantane having a CH 2 ═C(R)COO group(wherein R is a hydrogen atom, a methyl group or a trifluoromethyl group) at the 1-position, at each of the 1- and 3-positions, at each of the 1-, 3- and 5-positions, at each of the 1-, 3-, 5- and 7-positions, or at the 2-position.

TECHNICAL FIELD

The present invention relates to a novel perfluoroadamantyl compound andan intermediate therefor, and more particularly, to a novelperfluoroadamantyl compound and an intermediate therefor that are highlyuseful as a raw material for functional resins.

BACKGROUND ART

It is known that an acrylic ester and a methacrylic ester each having anadamantane skeleton can be polymerized into a polymer which is excellentin heat resistance, mechanical strength such as impact resistance andsurface hardness and optical characteristics. For instance, JapanesePatent Laid-Open Application {No. 307844/1988 (Showa 63)} proposes adiacrylate and dimethacrylate having a halogen atom or a hydroky groupat each of the 5-position of the adamantane skeleton or at each of the7-position of the same. The acrylic ester and methacrylic ester eachhaving the above-mentioned structural unit, which are colorless andtransparent and have high a surface hardness and also large refractiveindex, are highly useful as a raw material for optical instruments andmembers such as lens, prisms, photosensitive materials, optical fiberand optical discs. In addition, the acrylic ester and methacrylic esteras mentioned above have each a surpassingly high melting point andsurface hardness as compared with the acrylic ester and methacrylicester that are being generally used, are highly useful as a material ofa heat resistant covering and forming for an acrylic ester andmethacrylic ester. However the aforesaid useful acrylic ester andmethacrylic ester suffer from a disadvantage of insufficienttransparency in a low wavelength region.

As mentioned hereinbefore, the acrylic ester and a methacrylic estereach having an adamantane skeleton which is imparted with a specificchemical structure are highly useful as a raw material for a functionalresin. However it is desired to develop an acrylic ester and amethacrylic ester which have any of various chemical structures andwhich are capable of being made into an acrylic ester and a methacrylicester, respectively that are enhanced in such functionality as opticalproperties and heat resistance.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a perfluoroadamantylacrylate compound which is highly useful as a material for functionalresins and the like; and an intermediate therefor.

As the result of intensive extensive research and investigationaccumulated by the present inventors in order to achieve the object asmentioned above, it has been found that a perfluoroadamantyl acrylatecompound having a specific chemical structure can achieve theabove-mentioned object. Thus the present invention has been accomplishedon the basis of the foregoing findings and information.

Specifically, the gist of the present invention is as follows.

(1) A perfluoroadamantyl acrylate compound represented by the followinggeneral formula (1)

wherein R¹ is a hydrogen atom, a methyl group or a trifluoromethylgroup; X is a fluorine atom, a hydroxy group or a CH₂═C(R)COO group,wherein R is a hydrogen atom, a methyl group or a trifluoromethyl group;and m is an integer of from 12 to 15.

(2) A perfluoroadamantyl acrylate compound represented by the followinggeneral formula (2)

wherein R¹ is a hydrogen atom, a methyl group or a trifluoromethylgroup; and R 2 is a hydrogen atom, a methyl group, an ethyl group or aperfluoroalkyl group having 1 to 4 carbon atoms.

(3) A perfluoroadamantanol compound represented by the following generalformula (3)

wherein R³is a methyl group, an ethyl group or a perfluoroalkyl grouphaving 1 to 4 carbon atoms.

THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION

The perfluoroadamantyl acrylate compound according to the presentinvention is that represented by the above-mentioned general formula (1)or (2). Moreover the perfluoroadamananol compound according to thepresent invention is an intermediate (starting raw material) of theperfluoroadamantyl acrylate compound represented by the above-mentionedgeneral formula (2), and is represented by the above-mentioned generalformula (3). Herein, examples of the perfluoroalkyl group which isrepresented by R²or R³ and has 1 to 4 carbon atoms include atrifluoromethyl group, a pentafluoroethyl group, a heptafluoropropylgroup and a nonafluorobutyl group.

The perfluoroadamantyl acrylate -compounds represented by the generalformula (1) according to the present invention are specificallyexemplified by

The perfluoroadamantyl acrylate compounds represented by the generalformula (2) according to the present invention are specificallyexemplified by

The perfluoroadamantyl acrylate compounds represented by the generalformula (3) according to the present invention are specificallyexemplified by 2-methyl-2-perfluoroadamantanol,2-ethyl-2-perfluoroadamantanol,2-trifluoromethyl-2-perfluoroadamantanol,2-pentafluoroethyl-2-perfluoroadamantanol,2-heptafluoropropyl-2-perfluoroadamantanol, and2-nonafluorobutyl-2-perfluoroadamantanol.

Next, a process for producing a perfluoroadamantyl acrylate compoundrepresented by the general formula (1) can be in accordance with aprocess which comprises azeotropically dehydrating aperfluoroadamantanol and an acrylic acid or an analog thereof underreflux of a solvent. Examples of the perfluoroadamantanol to be used asa starting raw material include perfluoro-1-adamantanol,perfluoro-1,3-adamantandiol, perfluoro-1,3,5-adamantantriol andperfluoro-1,3,5,7-adamantantetraol. Examples of the acrylic acid or ananalog thereof include acrylic acid, methacrylic acid andα-trifluoromethyl acrylate. As a reaction solvent, toluene and xyleneare preferably used.

In addition, the reaction conditions in this case, which are similar tothose in a general azeotropical dehydration reaction, can be set on areaction temperature in the range of minus 78 to 200° C., but ispreferably set on the boiling point of the solvent at the reactionpressure at this time, including a reaction pressure in the range of 0.1to 10 MPa, a reaction time in the range of 1 to 24 hours, preferably 3to 6 hours. The concentration of the starting raw material to bedissolved in the reaction solvent needs only to be within the saturatedsolubility without specific limitation, but is preferably in the rangeof 0.5 to 1.0 mol/liter.

In a process for producing the perfluoroadamantyl acrylate compoundrepresented by the general formula (2) according to the presentinvention, the starting raw material needs only to use aperfluoroadamantanol such as

2-H-2-perfluoroadamantanol, 2-methyl-2-perfluoroadamantanol,

2-ethyl-2-perfluoroadamantanol, 2-trifluoromethyl-2-perfluoroadamantanoland

2-pentafluoroethyl-2-perfluoroadamantanol, and the reaction conditionsin this case need only to be similar to the foregoing.

Further, the reaction of the perfluoroadamantanol and the acrylic acidor analogues in the production of these perfluoroadamantyl acrylatecompounds may be put into practice by dehydration esterification by theuse of a dehydrating agent. In the case of this production process, thedehydrating agent is preferably selected for use from molecular sievesthat are used for general dehydration esterification and acidicdehydrating agents such as sodium sulfate anhydride, magnesium sulfateanhydride and phosphoric acid anhydride. As a reaction solvent, use ismade of an ether base solvent such as diethyl ether, tetrahydrofuran anddioxane; and an aliphatic hydrocarbon base solvent such as hexane,heptane and octane; and aromatic hydrocarbon base solvent such asbenzene, toluene and xylene. In addition, the reaction conditions inthis case can be set on a reaction temperature in the range of minus 78to 200° C., but is preferably set in the range of room temperature tothe boiling point of the solvent at the reaction pressure at this time,including a reaction pressure in the range of 0.1 to 10 MPa, preferablyatmospheric pressure, a reaction time in the range of 1 to 24 hours,preferably 3 to 6 hours. The concentration of the starting raw materialto be dissolved in the reaction solvent needs only to be within thesaturated solubility without specific limitation, but is preferably inthe range of 0.5 to 1.0 mol/liter.

The perfluoroadamantyl acrylate compounds can be produced byesterification reaction in the presence of a base between aperfluoroadamantanol and an acrylic acid chloride or an analog thereof.Examples of the base to be used therein include trimethylamine,triethylamine, pyridine and N,N-dimethylaniline. As a reaction solvent,which is not always necessary, use can be made of halogenatedhydrocarbons such as dichloromethane, carbon terachloride and1,2-dichloroethane; an ether base solvent such as diethyl ether,tetrahydrofuran and dioxane; and an aliphatic hydrocarbon base solventsuch as hexane, heptane and octane; and aromatic hydrocarbon basesolvent such as benzene, toluene and xylene. In addition, the reactionconditions in this case can be set on a reaction temperature in therange of minus 78 to 100° C., but is preferably set in the range ofminus 78 to room temperature, including a reaction pressure in the rangeof 0.1 to 10 MPa, a reaction time in the range of 1 to 24 hours,preferably 1 to 3 hours. In the case where a reaction solvent is used,the concentration of the starting raw material to be dissolved in thereaction solvent needs only to be within the saturated solubilitywithout specific limitation, but is preferably in the range of 0.5 to1.0 mol/liter.

The perfluoroadamantyl acrylate compounds can be produced byesterification reaction between a perfluoroadamantyl alkoxide and anacrylic acid chloride or an analog thereof. As a reaction solvent, usecan be made of an aliphatic hydrocarbon base solvent such as hexane,heptane and octane; and aromatic hydrocarbon base solvent such asbenzene, toluene and xylene. In addition, the reaction conditions inthis case can be set on a reaction temperature in the range of minus 78to 100° C., but is preferably set in the range of minus 78 to roomtemperature, including a reaction pressure in the range of 0.1 to 10MPa, a reaction time in the range of 1 to 24 hours, preferably 1 to 3hours. In the case where a reaction solvent is used, the concentrationof the starting raw material to be dissolved in the reaction solventneeds only to be within the saturated solubility without specificlimitation, but is preferably in the range of 0.5 to 1.0 mol/liter.

The perfluoroadamantyl alkoxide to be used in the reaction can beproduced by reacting the above-mentioned perfluoroadamantanol with analkoxiding agent. As the alkoxiding agent, use is made of metalliclithium, metallic sodium, metallic potassium, n-butyllithium,sec-butyllithium, tert-butyllithium, sodium hydroxide, sodium hydride,sodium boron hydride and lithium-alumnum hydride. As a reaction solvent,use is made of an ether base solvent such as diethyl ether,tetrahydrofuran and dioxane; an aliphatic hydrocarbon base solvent suchas hexane, heptane and octane; and aromatic hydrocarbon base solventsuch as benzene, toluene and xylene.

The acrylic acid chloride or an analog thereof to be used in thereaction can be produced by reacting a chlorinating agent with theabove-mentioned acrylic acid chloride or an analog thereof. As thechlorinating agent, there are preferably used thionyl chloride,phosphorus pentachloride, phosphorus trichloride, benzoic acid chlorideand phthalic acid chloride. In this reaction, as a reaction solvent,which is not always necessary, use can be made of halogenatedhydrocarbons such as dichloromethane, chloroform, carbon terachlorideand 1,2-dichloroethane; an aliphatic hydrocarbon base solvent such ashexane, heptane and octane; and aromatic hydrocarbon base solvent suchas benzene, toluene and xylene. There may be used as necessary, acatalyst such as N,N-dimethylformamide, hexamethylphosphoric triamideand pyridine; and a reaction accelerator such as benzyltriethylammoniumchloride.

In addition, the reaction conditions in this case can be set on areaction temperature in the range of 0 to 200° C., preferably roomtemperature to 100° C., including a reaction pressure in the range of0.1 to 10 MPa, a reaction time in the range of 1 to 24 hours, preferably1 to 6 hours. In the case where a reaction solvent is used, theconcentration of the starting raw material to be dissolved in thereaction solvent needs only to be within the saturated solubilitywithout specific limitation, but is preferably in the range of 0.5 to1.0 mol/liter.

In the last place, description will be given of some processes forproducing the perfluoroadamantanol represented by the general formula(3), wherein perfluoro-2-adamantanone is used in every case as astarting raw material.

(1) In the Case of R³ Being a Methyl Group or an Ethyl Group

(a) Addition Reaction to Carbonyl Group with a Grignard Reagent

The starting raw material and the Grignard reagent are reacted in asolvent and the reaction product is hydrolyzed with an acid. As areaction solvent, use is made of an ether base solvent such as diethylether, tetrahydrofuran and dioxane; an aliphatic hydrocarbon basesolvent such as hexane, heptane and octane; and aromatic hydrocarbonbase solvent such as benzene, toluene and xylene. As a Grignard reagent,use is made of an alkyl magnesium chloride (RMgCl), alkyl magnesiumbromide (RMgBr) and alkyl magnesium iodide (RMgI). The reactionconditions in the first half stage include atmospheric pressure,reaction temperature in the range of minus 78 to 200° C., preferably 0°C. to room temperature, a reaction time in the range of 1 to 24 hours.In the case where a reaction solvent is used, the concentration of thestarting raw material to be dissolved in the reaction solvent needs onlyto be within the saturated solubility without specific limitation, butis preferably in the range of 0.5 to 1.0 mol/liter.

(b) Addition Reaction to Carbonyl Group with a Lithium Reagent

The starting raw material and the lithium reagent are reacted in asolvent and the reaction product is hydrolyzed with an acid. As areaction solvent, use is made of an ether base solvent such as diethylether, tetrahydrofuran and dioxane; an aliphatic hydrocarbon basesolvent such as hexane, heptane and octane; and aromatic hydrocarbonbase solvent such as benzene, toluene and xylene. As a lithium reagent,use is made of an alkyl lithium (RLi) and dialkylmethylmagnesium cuprate(R₂LiCu). The reaction conditions in the first half stage includeatmospheric pressure, reaction temperature in the range of minus 78 to200° C., preferably 0° C. to room temperature, a reaction time in therange of 1 to 24 hours. In the case where a reaction solvent is used,the concentration of the starting raw material to be dissolved in thereaction solvent needs only to be within the saturated solubilitywithout specific limitation, but is preferably in the range of 0.5 to1.0 mol/liter.

(2) In the Case of R³ Being Rf (perfluoroalkyl group: CF₃˜C₄F₉)

(a) Addition Reaction to Carbonyl Group with a trimethylsilanylperfluoroalkane [RfSi(CH₃)₃]

The starting raw material and the trimethylsilanyl perfluoroalkane[RfSi(CH₃)₃] are reacted in a solvent in the presence of a catalyst, andthe reaction product is hydrolyzed with an acid. As a reaction solvent,use is made of an ether base solvent such as diethyl ether,tetrahydrofuran and dioxane; an aliphatic hydrocarbon base solvent suchas hexane, heptane and octane; and aromatic hydrocarbon base solventsuch as benzene, toluene and xylene. As a catalyst, use is made oftetrabutylammonium fluoride [(C₄H₉)₄NF]. The reaction conditions in thefirst half stage include atmospheric pressure, reaction temperature inthe range of usually minus 78 to 200° C., preferably 0° C. to roomtemperature, a reaction time in the range of usually 1 to 24 hours. Inthe case where a reaction solvent is used, the concentration of thestarting raw material to be dissolved in the reaction solvent needs onlyto be within the saturated solubility without specific limitation, butis preferably in the range of 0.5 to 1.0 mol/liter.

(b) Addition Reaction to Carbonyl Group with a perfluoroalkyl iodide(RfI)

The starting raw material and the perfluoroalkyl iodide (RfI) arereacted in a solvent in the presence of a catalyst, and the reactionproduct is hydrolyzed with an acid. As a reaction solvent, use is madeof an ether base solvent such as diethyl ether, tetrahydrofuran anddioxane; an aliphatic hydrocarbon base solvent such as hexane, heptaneand octane; N,N-dimethylformamide and dimethylsulfoxide. As a catalyst,use is made of Zinc (Zn)/dicyclopentadienyltitanium dicloride (Cp₂TiCl₂)(coexisting system). The reaction conditions in the first half stageinclude atmospheric pressure, reaction temperature in the range ofusually minus 78 to 200° C., preferably 0° C. to 100° C., a reactiontime in the range of usually 1 to 24 hours. In the case where a reactionsolvent is used, the concentration of the starting raw material to bedissolved in the reaction solvent needs only to be within the saturatedsolubility without specific limitation, but is preferably in the rangeof 0.5 to 1.0 mol/liter. It is preferable in this reaction tosimultaneously apply ultrasonic activation by means of a ultrasoniccleaner.

The perfluoroadamantyl acrylate compound obtainable in theabove-mentioned manner according to the present invention is excellentin such characteristics as heat stability, chemical stability, lubricityand electrical insulation properties and thus is highly useful in widefields of raw materials for functional resins required of opticalproperties and heat resistance; resin additives such as heat resistanceimprovers; additives such as acidity enhancers and fat-solubilityenhancers; coating materials such as paint and printing ink; lubricatingoil; working oil; heating/heat transfer media; adhesives; coveringmaterials for optical fiber; pharmaceuticals; agrochemicals;intermediates and so forth.

EXAMPLE

In what follows, the present invention will be described in more detailwith reference to comparative examples and working examples, whichhowever shall never limit the present invention thereto.

Example 1

In a 50 milliliter (mL) flask was placed 2.1 g (5.0 millimol) ofperfluoroadamantanediol and then were added 10 mL of tetrahydrofuran asa solvent and 0.84 mL (6.0 millimol) of triethylamine as a base withstirring. Subsequently the flask was put in an ice bath, and 0.4 mL (5.0millimol) of acrylic acid chloride was gradually added dropwise in theflask. When the acrylic acid chloride was added dropwise, a salt wasimmediately formed, causing the reaction liquid to become whitelyturbid. After the lapse of 15 minutes from the end of the dropwiseaddition, the flask was taken out from the ice bath, and the mixturetherein was reacted for 3 hours at room temperature with stirring. Afterthe completion of the reaction, the resultant reaction liquid wasfiltered with a cannula equipped with a filter, and the inside of theflask was washed twice with 5 mL of tetrahydrofuran. Subsequently thesolvent was evaporated away from the reaction liquid. Thus the reactionliquid was purified with a glass tube oven to obtain the objectiveperfluoro-1-adamantyl acrylate with a yield amount of 1.4 g(2.9millimol) and a yield rate 59.0%.

As a result of analysis for the resultant perfluoro-1-adamantyl acrylateby nuclear magnetic resonance spectra (NMR), there were observed thefollowing absorption.

¹H-NMR {270 MHz}: at 6.16 (dd, J_(vic-trans)=10.4 Hz, J_(gem)=1.5 Hz,1H), 6.25 (dd, J_(vic-trans)=10.4 Hz, J_(vis-cis)=16.3 Hz, 1H), 6.64(dd, J_(vic-cis)=16.3 Hz, J_(gem)=1.5 Hz, 1H). ¹³C-NMR {68 MHz}: at123.4, 136.12, 157.47. ¹⁹F-NMR {254 MHz}: at −221.55 (s, 3F), −121.17(s, 6F), −114.62 (s, 6F).

In addition, the results of gas-chromatography mass spectrometricanalysis were 476 (M⁺, 2.4%), 456 (1.8%), 55 (100%).

Example 2

The procedure in Example 1 was repeated to obtain the objectiveperfluoro-1-adamantyl acrylate except that 0.49 mL (5.0 millimol) ofmethacrylic acid chloride was used in place of the acrylic acid chlorideas the starting raw material. The yield amount was 1.6 g (3.3 millimol)and yield rate 65.0%.

As a result of analysis for the resultant perfluoro-1-adamantyl acrylateby nuclear magnetic resonance spectra (NMR), there were observed thefollowing absorption.

¹H-NMR {270 MHz}: at 3.03 (s, 3H), 5.88 (s 1H), 6.33 (s, 1H). ¹³C-NMR{68 MHz}: at 18.34, 130.46, 158.79. ¹⁹F-NMR {254 MHz}: at −221.65 (s,3F), −121.18 (s, 6F), −114.55 (s, 6F).

In addition, the results of gas-chromatography mass spectrometricanalysis were 490 (M⁺, 20%), 471 (19%), 69 (100%).

Example 3

(1) Production of α-(trifluoromethyl)acrylic acid chloride

In a 200 mL flask was placed 42.0 g (300 millimol) ofα-(trifluoromethyl) acrylic acid, to which was gradually added 70.0 mL(450 millimol) of phthalic dichloride at room temperature with stirring.Subsequently, by reacting the contents in the flask for 2 hours, whileheating in an oil bath at 135° C., an orange reaction liquid wasobtained.

Subsequently, by atmospherically distillating the reaction liquid, 41.2g (yield rate 86.6%) of colorless transparent product in liquid form wasobtained.

As a result of analysis for the resultant perfluoro-1-adamantyl acrylateby nuclear magnetic resonance spectra (NMR), there were observed thefollowing absorption.

¹H-NMR {270 MHz}: at 6.91 (s, 1H), 7.11 (s, 1H). ¹³C-NMR {68 MHz}: at120.91 (quar, J_(C-F)=273.9 Hz), 135.25 (quar, J_(C-CF3)=31.8 Hz),139.28, 161.92.

Thereby, the colorless transparent product was identified asα-(trifluoromethyl)acrylic acid chloride.

(2) Production of perfluoro-1-adamantyl-α-(trifluoromethyl) acrylate

The procedure in Example 1 was repeated to obtain the objectiveperfluoro-1-adamantyl-α-(trifluoromethyl) acrylate except that 801 mg(5.1 millimol) of the α-(trifluoromethyl) acrylic acid chloride whichhad been obtained in the preceding item (1).

The yield amount was 1.2 g (2.2 millimol) and yield rate was 44%.

As a result of analysis for the resultantperfluoro-1-adamantyl-α-(trifluoromethyl) acrylate by nuclear magneticresonance spectra (NMR), there were observed the following absorption.

¹H-NMR {270 MHz}: at 7.92 (quar, J=2.8 Hz, 1H), 8.04 (quar, J=2.8 Hz,1H) ¹³C-NMR {68 MHz}: at 121.15 (quar, J_(C-F)=268.5 Hz), 131.85 (quar,J_(C-CCF3)=5.0 Hz), 132.74 (quar, J_(C-CF3)=31.8 Hz), 159.79. ¹⁹F-NMR{254 MHz}: at −221.51 (s, 3F), −121.99 (s, 6F), −114.44 (s, 6F), −66.41(s, 3F)

In addition, the results of gas-chromatography mass spectrometricanalysis were 544 (M⁺, 5.4%), 523 (4.3%), 123 (100%).

Example 4

(1) Production of 2-methyl-2-perfluoroadamantanol

In a 500 mL Kjeldahl flask was placed 24.1 g (60 millimol) of2-perfluoroadamantanone, to which was added 180 mL of dry diethyl etherto dissolve the same. Thereafter the flask was put in an ice bath and 21mL (63 millimol) of 3 mol/liter solution of methylmagnesium bromide wasadded dropwise in the flask with stirring. After the lapse of 30minutes, gas-chromatographic analysis was carried out with a result thatthe disappearance of the raw material peak was confirmed. After thereaction liquid was poured on ice water, dilute hydrochloric acid wasadded so as to dissolve inorganic substances in a water phase. Organicphase was separated with a separatory funnel and dried. Then byevaporating away the solvent, 22.9 g of a crude product was obtained,purified with a column, and recrystallized from methanol-hexane toobtain the objective product.

The yield amount was 8.1 g (19.4 millimol) and yield rate was 32.3%.Purity measured by gas chromatography was 84.1% [area].

As a result of analysis for the resultant2-methyl-2-perfluoroadamantanol by nuclear magnetic resonance spectra(NMR), there were observed the following absorption.

¹H-NMR {500 MHz}: at 1.81 (s, 3H, CH₃), ¹³C-NMR {126 MHz}: at 19.68 (t,J=13.2 Hz, CH₃) ¹⁹F-NMR {471 MHz}: at −223.11 (s, 1F, d or e),−222.71(s, 1F d or e), −217.94 (s, 2F, a), −123.62 (quar,J=240 Hz, 1F),−121.11 (s, 2F, f), −118.52 (d,j=240 Hz, 1F), −117.46 (s, 1F), −116.90(s, 1F), −116.34 (s, 1F), −114.39 (d,j=271 Hz, 2F)

In addition, the results of gas-chromatography mass spectrometricanalysis were 418 (M⁺, 0.38%), 403 (6.0%), 131 (85.2%), 69 (100%).

The melting point measured by DSC (differential scanning calorimetry)was 69.7 to 79.5° C.

As the result of structural analysis by the above-mentioned spectoscopicdata, the following structural formula has been confirmed.

(2) Production of 2-methyl-2-perfluoroadamantyl methacrylate

In a 50 mL Kjeldahl flask was placed 0.836 g (2.0 millimol) of2-methyl-2-perfluoroadamantanol, to which was added 20 mL oftetrahydrofuran to dissolve the same. Thereafter the flask was put in anice bath, and 0.33 mL (2.4 millimol) of triethylamine and 0.22 mL (2.0millimol) of methacrylic acid chloride were added in the flask to startstirring. After the lapse of 15 minutes, the ice bath was taken out, andthe contents therein were reacted for further 48 hours at roomtemperature. The reaction liquid was filtered with fluted filter paper,and the flask was washed twice with 5 mL of diethyl ether. Salts wereremoved from the reaction liquid with a separatory funnel to recoverorganic phase. Then by distilling away the solvent and purifying with acolumn, the objective 2-methyl-2-perfluoroadamantyl methacrylate wasobtained,

The yield amount was 0.17 g (0.35 millimol) and yield rate was 17.5%.Purity measured by gas chromatography was 97.6% [area].

As a result of analysis for the resultant 2-methyl-2-perfluoroadamantylmethacrylate by nuclear magnetic resonance spectra (NMR, CDCl₃), therewere observed the following absorption.

¹H-NMR {500 MHz}: at 1.93 (s, 3H, f), 2.16 (s, 3H, c), 5.71 (s, 1H, a1),6.12 (s, 1H, a2) ¹³C-NMR {126 MHz}: at 15.04 (f), 18.31(c), 128.54 (a),130.50(b), 162.32(d). ¹⁹F-NMR {471 MHz}: at −221.65 (s, 3F),−121.18 (s,6F), −225.55 (s, 2F, g or j) −209.76 (s, 2F, j or g), −121.07 (s, 2F,k), −116.72(q, 6F,i), −114.03 (d, 2F, h)

In addition, the results of gas-chromatography mass spectrometricanalysis were 486 (M⁺, 1.4%), 400 (1.4%), 381 (2.4%), 181 (7.1%), 86(100%).

The melting point measured by DSC (differential scanning calorimetry)was 54.7 to 57.1° C.

As the result of structural analysis by the above-mentioned spectoscopicdata, the following structural formula has been confirmed.

Example 5

In a 500 mL Kjeldahl flask was placed 62.3 g (150 millimol) of1,3-perfluoroadamantandiol¹⁾, to which was added 200 mL of diethy etherto dissolve the same. Thereafter the flask was put in an ice bath, and25.1 mL (180 millimol) of triethylamine and 12.2 mL (150 millimol) ofmethacrylic acid chloride were added in the flask to start stirring.After the lapse of 1 hour, the ice bath was taken out, and the contentstherein were reacted for further 15 hours at room temperature. Thereaction liquid was filtered with fluted filter paper, and the flask waswashed twice with 50 mL of diethyl ether. Salts were removed from thereaction liquid with a separatory funnel to recover organic phase. Thenby evaporating away the solvent and purifying with a column, theobjective 3-hydroxy-1-perfluoroadamantyl acrylate²) [actual yield amountof 18.6 g (39.2 millimol), yield rate of 26.1% and purity measured bygas chromatography being 96.5% {area}] and 1,3-perfluoroadamantyldiacrylate [actual yield amount of 8.6 g (16.2 millimol), yield rate of10.8% and purity measured by gas chromatography being 95.3% {area}] wereobtained,

-   1): contains 2-hydro-1,3-perfluoroadamantandiol by 25.4% as an    impurity.-   2): 3-hydroxy-1-perfluoroadamantyl acrylate and    1,3-perfluoroadamantyl diacrylate contain as impurities,    2-hydro-3-hydroxy-1-perfluoroadamantyl acrylate by 10.7% and    2-hydro-1,3-perfluoroadamantyl diacrylate by 18.7%, respectively.

As a result of analysis for the resultant 3-hydroxy-1-perfluoroadamantylacrylate by nuclear magnetic resonance spectra (NMR, CDCl₃), there wereobserved the following absorption.

¹H-NMR {500 MHz}: at 4.95 (br, 1H,), 6.14 (d,J=10.1 Hz, 1H), 6.24(dd,J=10.1 Hz, 1H, J=17.2 Hz, 1H,), 6.62 (J=17.2 Hz, 1H,) ¹³C-NMR {126MHz}: at 125.88 (CH₂═), 135.96(—CH═), 158.05 (C═O), ¹⁹F-NMR {471 MHz}:at −219.30 (s, 2F), −120.69 (s, 6F), −113.61 (s, 6F)

In addition, as the results of infrared spectroscopy (IR), absorptionwas observed at 1765.6 cm⁻¹ (C═H).

The melting point measured by DSC (differential scanning calorimetry)was 69.7 to 79.5° C.

As a result of analysis for the resultant 1,3-perfluoroadamantyldiacrylate by nuclear magnetic resonance spectra (NMR, CDCl₃), therewere observed the following absorption.

¹H-NMR {500 MHz} . . . at 6.12 (d,J=10.9 Hz, 2H), 6.24 (d,d, J=10.9 Hz,J=16.6 Hz, 2H), 6.62 (J=16.6 Hz, 2H) ¹³C-NMR {126 MHz}: at 126.09(CH₂═), 135.78 (—CH═), 161.55 (C═O), ¹⁹F-NMR {471 MHz}: at −219.01 (t,J=29 Hz, 2F), −121.19 (s, 2F), −120.49(d,J=249 Hz, 2F), −119.07 (d,J=264Hz, 2F),−117.19(d,J=249 Hz, 2F), −113.81 (d,J=29 Hz, 2F),−113.49(d,J=264 Hz, 2F)

In addition, as the results of infrared spectroscopy (IR), absorptionwas observed at 1781.8 cm⁻¹(C═H).

The melting point measured by DSC (differential scanning calorimetry)was 92.4 to 106.7° C.

INDUSTRIAL APPLICABILITY

The present invention can provide a perfluoroadamantyl acrylate compoundwhich is highly useful in wide fields of raw materials for functionalresins required of optical properties and heat resistance; resinadditives such as heat resistance improvers; additives such as acidityenhancers and fat-solubility enhancers; coating materials such as paintand printing ink; lubricating oil; working oil; heating/heat transfermedia; adhesives; covering materials for optical fiber; pharmaceuticals;agrochemicals; intermediates and so forth.

1. A perfluoroadamantyl acrylate compound represented by the followinggeneral formula (1)

wherein R¹ is a hydrogen atom, a methyl group or a trifluoromethylgroup; X is a fluorine atom, a hydroxy group or a CH₂═C(R)COO group,wherein R is a hydrogen atom, a methyl group or a trifluoromethyl group;and m is an integer of from 12 to
 15. 2. A perfluoroadamantyl acrylatecompound represented by the following general formula (2)

wherein R¹ is a hydrogen atom, a methyl group or a trifluoromethylgroup; and R² is a hydrogen atom, a methyl group, an ethyl group or aperfluoroalkyl group having 1 to 4 carbon atoms:
 3. Aperfluoroadamantanol compound represented by the following generalformula (3)

wherein R³ is a methyl group, an ethyl group or a perfluoroalkyl grouphaving 1 to 4 carbon atoms.